Lösliche trans ‐Di‐1‐alkinyl‐ und Poly‐ trans ‐ethinyl(tetraalkylphthalocyaninato)metall‐IVB‐Derivate

Abstract

Die bislang unbekannten peripher substituierten trans-Dihalogeno(tetra-tert-butylphthalocyaninato)metall-IVB-Derivate 5a, b und 6a, b sowie trans-Dichloro[tetrakis(trimethylsilyl)phthalocyaninato]germanium (6c) wurden durch Umsetzung mit verschiedenen 1-Alkinyl-Grignardverbindungen 9a -e in die monomeren trans-Di-l-alkinyl(tetra-tert-butylphtha1ocyaninato)-metall-IVB-Derivate 10a -h bzw. trans-Di-l-alkinyl[tetrakis(trimethylsilyl)phthalocyaninato]-germanium-Derivate 1Oi -I ubergefuhrt. Die gute Loslichkeit aller Produkte und der starke, auf die axial gebundenen Liganden wirkende Ringstromeffekt des Makrocyclus sind bemerkenswert.Die formal analoge Umsetzung mit der zweizahnigen Ethindiyldi-Grignardverbindung 9f fuhrt zu den acetylenverbruckten Polymeren 12a -c. Diese sind Modellsubstanzen fur einen von uns vorgeschlagenen neuartigen Typ eines eindimensionalen Leiters. Soluble trans-Di-1-alkynyl-and Poly-trans-ethynyl(tetraalkylphthalocyaninato)me~l IVB DerivativesThe hitherto unknown peripheric substituted trans-dihalogeno(tetra-?erf-butylphthalocyaninato)-metal IVB derivatives 5a, b and 6a, b as well as trans-dichloro[tetrakis(trimethylsilyl)phthalocyaninato]germanium (6c) were converted into the monomeric, soluble trans-di-1 -alkynyl(tetratert-butylphtha1ocyaninato)metal IVB compounds 10a -h and trans-di-1-alkynyl[tetrakis(trimethylsilyl)phthalocyaninato]germanium compounds 1Oi -1, respectively, by the reaction with various 1-alkynyl Grignard derivatives 9a -e. The high solubility of all products in organic solvents and the strong ring-current effect of the macrocycle on the axial ligands are remarkable. The formally analogous reaction with the bidentate ethynediyldi-Grignard compound 9f leads to the soluble, acetylene-bridged polymers 12a -c. These are considered as model compounds for a new kind of one-dimensional conductors proposed by us.Vor einiger Zeit stellten wir ein Konzept fur einen neuen organischen Leiter vor '), bei dem makrocyclische Metallkomplexe uber Bruckenliganden zu polymeren Strukturen verknupft sind. Das Strukturkonzept zeichnet sich durch eine grooe Variationsbreite hinsichtlich der erforderlichen Komponenten -Zentralmetall, Makrocyclus und Briickenligand -aus. EHMO-Berechnungen zu einem Modellsystem haben ergeben'), da13 beim Ubergang vom Monomeren zum Polymeren mit einer erheblichen Steigerung der elektrischen Leitfahigkeit entlang der Polymerenachse zu rechnen ist.Obwohl es bisher lediglich gelungen ist, monomere Modellsubstanzen des berechneten Polymeren zu synthetisieren 3), haben erste Untersuchungen an strukturell ahnli-0

Incorporation of Differently Substituted Phthalocyanines into the Mesoporous Molecular Sieve Si-MCM-41

“…Yield 1.48 g (27%). 4-tert-Butylphthalonitrile [34] (E9) (500 mg, 2.7 mmol) was dissolved in 20 ml dry 1-pentanol and the solution was heated at 140°C under stirring and reflux. Elemental lithium (100 mg, 14 mmol) was added and the solution was stirred for 30 min.…”

Double-decker lutetium(III) diphthalocyanine with eight crown ether substituents

“…The product was soluble in dichloromethane, chloroform, acetic acid and DMSO. methyl-3,4-dibromobenzene which was further converted into the o-dicyano derivative 1 by the Rosenmund von Braun reaction [13][14][15][16][17].…”

Multisubstituted phthalonitriles for phthalocyanine synthesis

“…The synthesis of sy.mmetrical tetra [3][4][5][6], oct^ 17-91, and even hexadecaphthalocyanine (Pcs) [10][11][12] are relatively straightforward using an appropriately substituted phthalonitrile as the sole precursor. In most examples these phthalonitrile precursors consist of phthalonitriles containing only one substituent at the 3-or 4-position or disubstituted phthalonitriles having two identical substituent$ on the 4,5-or 3,6-positions, but in one unusual example at the 3,4-position [3].…”

“…Following the procedure described for 8 below, but using 3j, 5,6-tetrafluorophthalonitrile (l), and p-methylphenol (4), a product was obtained which was chromatographed on flash grade silica gel using ethyl acetate I hexane (l:l) 3,4,6-trichloro-5-p.methylphenoxyphthalonitrile (9). Following the procedure described for 8 above, but using 3,4,5,6-tetrachlorophthalonitrile (2), and p-methylphenol (4) 3,4,6-trichloro-5-p-nitrophenoxyphthalonitrile (10). Following the procedure described for g above.…”